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CN103874541A - Oxidation catalyst for internal combustion engine exhaust gas treatment - Google Patents

Oxidation catalyst for internal combustion engine exhaust gas treatment Download PDF

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Publication number
CN103874541A
CN103874541A CN201280049001.4A CN201280049001A CN103874541A CN 103874541 A CN103874541 A CN 103874541A CN 201280049001 A CN201280049001 A CN 201280049001A CN 103874541 A CN103874541 A CN 103874541A
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CN
China
Prior art keywords
washcoat
piece
substrate material
catalyst
platinum
Prior art date
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Granted
Application number
CN201280049001.4A
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Chinese (zh)
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CN103874541B (en
Inventor
P·布莱克曼
G·M·布朗
S·查特吉
A·F·希菲
J·加斯特
H·奥亚马达
P·R·菲利普斯
R·R·拉杰拉姆
角屋聪
汪利峰
A·沃克
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Johnson Matthey PLC
Johnson Matthey Japan GK
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Johnson Matthey PLC
Johnson Matthey Japan GK
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Priority claimed from GB1200786.0A external-priority patent/GB2497598A/en
Application filed by Johnson Matthey PLC, Johnson Matthey Japan GK filed Critical Johnson Matthey PLC
Priority to CN201611239990.XA priority Critical patent/CN106622352B/en
Publication of CN103874541A publication Critical patent/CN103874541A/en
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/52712—Plural layers on a support, each layer having a distinct function

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Abstract

The invention provides an exhaust gas cleaning oxidation catalyst and in particular to an oxidation catalyst for cleaning the exhaust gas discharged from internal combustion engines of compression ignition type (particularly diesel engines). The invention further relates to a catalysed substrate monolith comprising an oxidising catalyst on a substrate monolith for use in treating exhaust gas emitted from a lean-burn internal combustion engine. In particular, the invention relates to a catalysed substrate monolith comprising a first washcoat coating and a second washcoat coating, wherein the second washcoat coating is disposed in a layer above the first washcoat coating.

Description

For the oxidation catalyst of engine exhaust gas processing
Invention field
The present invention relates to exhaust gas cleaning oxidation catalyst, and be particularly related to the oxidation catalyst for clean waste gas of being discharged by compression ignition type internal combustion engine (particularly Diesel engine).The invention further relates to the catalytic substrate material all in one piece that is included in the oxidation catalyst on substrate material all in one piece for the treatment of the waste gas being gone out by fuel-sean engine exhaust.Especially, the present invention relates to comprise the catalytic substrate material all in one piece of the first washcoat (washcoat coating) and the second washcoat, wherein the second washcoat is arranged in the layer on the first washcoat.The invention still further relates to the purposes of this catalytic substrate material all in one piece in the gas extraction system of fuel-sean internal combustion engine (particularly vehicular lean-burn internal combustion).
Background of invention
Conventionally, there are four pollutants to be limited by the legislation of global Intergovernmental Organization: carbon monoxide (CO), unburned hydrocarbon (HC), nitrogen oxide (NO x) and particle (PM).
Oxidation catalyst is for clearing up hydrocarbon (HC), carbon monoxide (CO) and the solubility organic principle (SOF) (referring to Japanese patent application publication No. 9-271674) in the waste gas being generated by compression ignition type internal combustion engine fuel combustion.Notice concentrates on again the filter (diesel particulate filter (DPF)) of processing the particle (PM) being generated by fuel combustion in compression ignition type internal combustion engine and can collecting PM recently.Oxidation catalyst has been arranged in the upstream portion of DPF to improve the treatment efficiency (referring to Japanese patent application publication No. 2006-272064) to DPF PM.
Contain more sulphur composition compared with the fuel package of heavy.In the compression-type internal combustion engine that uses diesel oil as fuel, in fuel combustion and catalytic process, discharge oxysulfide (SO x), the activity of oxidation catalyst is subject to SO xthe inhibition (sulfur poisoning) existing.For processing this problem, the oxidation catalyst of sulfur poisoning-resistant has been proposed, it has as the zeolite of the mixture of the ZSM-5 that comprises specified weight ratio and beta-zeolite (referring to Japanese patent application publication No. 2007-229679).In addition,, for cleaning exhaust gas more effectively, proposed to there is double-deck NO xclean catalysis agent, it comprises two different catalyst layers, i.e. NO xlayer of oxidation catalyst and NO xselective reduction catalyst layer (referring to Japanese patent application publication No. 2008-279352).
Along with the discharge standard that the tolerable of pollutant in the waste gas to from vehicle motor discharges is more and more stricter, propose and developed the combination of engine management and multi-catalyst exhausted gas post-processing system to meet these discharge standards.For the gas extraction system that comprises particulate filter, conventionally regularly (for example, every 500km) carries out engine management to improve temperature in filter to burn all remaining cigarette ash substantially remaining on this filter, thus this system returned to baseline values.These are through the soot combustion event so-called " filter regeneration " of engine management.Although being burning, the principal focal point of filter regeneration remains on the cigarette ash on this filter, but expected result was not according to the level of engine management in this system, the one or more catalyst coats (the filtration coating of for example filter (so-called catalysis soot filter (CSF)) itself) that exist in gas extraction system, oxidation catalyst (for example diesel oxidation catalyst (DOC)) or the NO that is positioned at filter upstream or downstream xadsorption catalyst (NAC) (being for example diesel particulate filter after a DOC, is again the 2nd DOC afterwards, is finally SCR catalyst) can regularly be exposed to high EGT.These conditions also may experience the undesired pattern of accidental engine (upset mode) of not expected or uncontrolled or control poor regeneration event.But, some Diesel engines heavy duty diesel engine of high load operation (particularly with) even can be under normal operating condition by catalyst exposure for example, in high temperature (>600 ℃).
Because vehicular manufacturer develops its engine and engine management system to meet discharge standard, the applicant/assignee is required the combination that proposes catalyst component and catalyst component to help to realize the target that meets discharge standard by vehicular manufacturer.These components comprise for being oxidized CO, HC and the optional DOC that is also oxidized NO; For be oxidized CO, HC, optionally be also oxidized NO and for trap particulate matter for the CSF with after-combustion; Be used for being oxidized CO and HC and absorb the also NO of desorption absorption for oxidization of nitric oxide (NO) with by it from poor waste gas xand it is reduced to N in rich waste gas 2nAC (below seeing); With for nitrogenous reducing agent (for example ammonia) exist under by NO xbe reduced to N 2sCR (SCR) catalyst (below seeing).
In practice, the carbon monoxide-olefin polymeric using in DOC and CSF is closely similar.But, conventionally the Main Differences between DOC and the use of CSF is the coated substrate material all in one piece of this carbon monoxide-olefin polymeric: in the situation of DOC, normally flow type substrate material all in one piece of this substrate material all in one piece, comprise having and extend metal or the ceramic honeycomb material all in one piece of elongated passageway array connecting, this passage is openings all at two ends; CSF substrate material all in one piece is that filter material all in one piece is as wall-flow filter, for example ceramic porous filter base, it comprises the multiple access roades that are arranged in parallel with multiple exit passageways, wherein each access road and each exit passageway are partly limited by the ceramic wall of loose structure, wherein each access road and exit passageway alternately separate by the ceramic wall of loose structure, and vice versa.In other words, wall-flow filter is cellular layout, define multiple upstream extremity stop up first passages and multiple upstream extremity do not stop up but downstream stop up second channel.Stop up in downstream with laterally adjacent passage with first passage is vertical.In the time observing from arbitrary end, the alternately obstruction of passage and the end of opening present the outward appearance of chessboard.
On flow type substrate material all in one piece, can apply very complicated multi-layer catalyst and arrange, for example DOC and NAC.For example, although can use the surface (the access road surface of wall-flow filter) more than the carbon monoxide-olefin polymeric filter application material all in one piece of one deck, but the problem of filter application material all in one piece is will avoid in use, by with catalyst activation coating this filter material all in one piece of excessive loads and unnecessarily improve back pressure, limiting thus gas communication.Therefore, although with the surface of one or more different catalyst layer sequential applications filter base materials all in one piece be not impossible, but more generally by different carbon monoxide-olefin polymeric compartmentalizations, the first half district of for example axial separation of filter material all in one piece and later half district, or by the access road with the first carbon monoxide-olefin polymeric coating wall-flow filter substrate material all in one piece, apply its exit passageway with the second carbon monoxide-olefin polymeric.But, in specific embodiment of the invention scheme, with one or more can be the layer filter application entrance of identical or different carbon monoxide-olefin polymeric.Also propose to apply NAC composition (for example, referring to EP0766993) on filtration substrate material all in one piece.
In the gas extraction system that comprises multiple catalysts component (including independent substrate material all in one piece), conventionally SCR catalyst is positioned at the downstream of DOC and/or CSF and/or NAC, because known to some nitric oxides (NO) in waste gas are oxidized to nitrogen dioxide (NO 2), make to leave the NO:NO of DOC and/or CSF and/or NAC 2than being about 1:1, promote the SCR reaction (below seeing) in downstream.From EP341832 (so-called cyclic regeneration trap or ) in also known, by the NO in waste gas is oxidized to NO 2and the NO producing 2can be used in the cigarette ash that burns passively in downstream filter.In the important gas extraction system of the method for EP341832 is arranged, if SCR catalyst is positioned at the upstream of filter, this will reduce or stop the cigarette ash of trapping at NO so 2the process of middle burning, because for the NO of the cigarette ash that burns xmajor part will on SCR catalyst, remove possibly.
But the preferred system layout of light diesel vehicle is that diesel oxidation catalyst (DOC) is nitrogenous reducing agent injector afterwards, is then SCR catalyst, is finally catalysis soot filter (CSF).This layout referred to as " DOC/SCR/CSF ".This layout is preferred for light diesel vehicle, because important consideration is to realize as quickly as possible NO after vehicle motor starts in gas extraction system xtransform, to guarantee that (i) for example, sprays/decompose to discharge ammonia for NO by the precursor of nitrogenous reducing agent (ammonia) xtransform; (ii) high as far as possible NO xconversion ratio.If large thermal mass filter is placed on to SCR catalyst upstream (being between DOC and SCR catalyst) (" DOC/CSF/SCR "), (i) process and (ii) will need the much longer time to realize, and drives the NO in cycle for whole discharge standard xconversion ratio will reduce.Can and adopt engine management techniques to realize particle to the forced regeneration once in a while of filter with oxygen removes.
Propose SCR catalyst activation coating to be coated in and to filter substrate material all in one piece from (for example, referring to WO2005/016497) with it, in this case, oxidation catalyst can be positioned at the upstream (the no matter whether component of DOC, CSF or NAC of this oxidation catalyst) of the filtration substrate that is coated with SCR, to improve NO/NO 2than being used for improving the NO on SCR catalyst xreducing activity.Also proposed NAC to be arranged on the SCR catalyst upstream being positioned on flow type substrate material all in one piece, this NAC can produce NH at the regenerative process situ of NAC 3(seeing following).A kind of this proposal is disclosed in GB2375059.
NAC is for example from US5, and 473,887 is known, and through design to adsorb NO from poor waste gas (λ >1) xand desorb this NO when oxygen concentration reduces in waste gas x.The NO of desorb xcan for example, be reduced into N with applicable reducing agent (engine fuel) 2, for example, promote by NAC self or the catalytic component (rhodium) that is positioned at NAC downstream.In practice, can be off and on according to the remaining NO of NAC calculating xadsorption capacity will be to the control and regulation of oxygen concentration to required redox composition, for example, than normal engine operation more fuel-rich (but still poor in the composition of stoichiometric or λ=1), stoichiometric or be imbued with stoichiometric (λ <1).Oxygen concentration can regulate by multiple means, for example throttling, for example, by other hydrocarbon fuel injection engine cylinder (in exhaust stroke process) or by the waste gas of direct hydrocarbon fuel injection engine header downstream.
The typical NAC NO that comprises catalytic oxidation component (for example platinum), significant quantity (being for example fully greater than, as the required amount of auxiliary agent (auxiliary agent in three-way catalyst)) that fills a prescription xstorage component (for example barium) and reducing catalyst (for example rhodium).For this formula, for storing NO from poor waste gas xcommon mechanism is:
NO+1/2O 2→ NO 2(1); With
BaO+2NO 2+1/2O 2→Ba(NO 3) 2 (2)，
Wherein, in reaction (1), nitric oxide reacts on the active oxidation position on platinum with oxygen and generates NO 2.Reaction (2) comprises the form absorption NO with inorganic nitrate by storage material 2.
In the time of the temperature of lower oxygen concentration and/or rising, this nitrate thing class becomes thermodynamic instability and decomposes, and generates NO or NO according to reaction (3) below 2.Under applicable reducing agent exists, these nitrogen oxide are reduced to N by carbon monoxide, hydrogen and hydrocarbon subsequently 2, can on reducing catalyst, there is (referring to reaction (4)) in this.
Ba (NO 3) 2→ BaO+2NO+3/2O 2or Ba (NO 3) 2→ BaO+2NO 2+ 1/2O 2(3); With
NO+CO→1/2N 2+CO 2 (4)；
(other reactions comprise Ba (NO 3) 2+ 8H 2→ BaO+2NH 3+ 5H 2o, then
NH 3+ NO x→ N 2+ yH 2o or 2NH 3+ 2O 2+ CO → N 2+ 3H 2o+CO 2deng).
In reaction (1)-(4) that comprise on herein, active barium thing class provides as oxide.But, being to be understood that under air exists, most of barium is carbonate or may is the form of hydroxide salt.Technical staff can adjust thus the order for catalyst coatings in the above-mentioned reaction scheme of other barium thing classes except oxide and waste gas streams.
Oxidation catalyst promotes that CO is oxidized to CO 2be oxidized to CO with unburned HC 2and H 2o.Typical oxidation catalyst is included in platinum and/or the palladium on high surface area carrier.
SCR technology is for the treatment of the NO of vehicle internal combustion (IC) engine (particularly fuel-sean IC engine) xthe application of discharge is known.Can comprise for example nitrogen hydride of compound, for example ammonia (NH for the example of the nitrogenous reducing agent in SCR reaction 3) or hydrazine or NH 3precursor.
NH 3precursor is for example to obtain NH by hydrolysis 3one or more compounds.Precursors decompose is that ammonia and other accessory substances can be undertaken by hydro-thermal or catalyzing hydrolysis.NH 3precursor comprises as the aqueous solution or as the urea (CO (NH of solid 2) 2) or aminoquinoxaline (NH 2cOONH 4).If be used as the urea of the aqueous solution, preferably eutectic mixture, for example 32.5%NH 3(moisture).In this aqueous solution, can comprise that additive is to reduce crystallization temperature.At present, urea is the preferred NH for mobile application 3source, because its toxicity compares NH 3low, it is easy to transportation and processes, and its is cheap and conventionally can obtain.In the test for meeting relevant emission testing circulation, the incomplete hydrolysis of urea can cause PM discharge to improve, because PM quality is caught and counted to the urea solid of partial hydrolysis or drop by being tested filter paper used by the legislature of PM.Further, being released on environment of some product (for example cyanuric acid) of incomplete urea hydrolysis is unfavorable.
SCR has three key reactions (being shown in reaction (5)-(7) that comprise) below, and it is by NO xbe reduced to simple substance nitrogen.
4NH 3+ 4NO+O 2→ 4N 2+ 6H 2o (is 1:1NH 3: NO) (5)
4NH 3+ 2NO+2NO 2→ 4N 2+ 6H 2o (is 1:1NH 3: NO x) (6)
8NH 3+ 6NO 2→ 7N 2+ 12H 2o (is 4:3NH 3: NO x) (7)
Relevant unfavorable non-selective side reaction is:
2NH 3+2NO 2→N 2O+3H 2O+N 2 (8)
In practice, reaction (7) is slow compared with (5) with reaction, and it is the fastest in all reacting (6).Therefore,, in the time of technical staff's design vehicle exhausted gas post-processing system, they are preferentially arranged on oxidation catalyst element (for example DOC and/or CSF and/or NAC) upstream of SCR catalyst conventionally.
User has made applicant/assignee notice, in the time that some DOC and/or NAC and/or CSF are exposed to the high temperature (for example, at filter regeneration and/or engine abnormal conditions and/or (in some heavy-duty diesel oil application) normal high-temp waste gas) running into, the enough time that can be provided in high temperature evaporates the platinum group metal component of low content (particularly Pt) from DOC and/or NAC and/or CSF component, and makes subsequently this platinum group metal be captured on the SCR catalyst in downstream.This can have height injurious effects to the performance of SCR catalyst, because the existence of Pt causes, to emulative non-selective ammoxidation, as the ammoxidation in reaction (9), (it has shown NH 3complete oxidation) there is high activity, produce thus secondary emission and/or unnecessary consumption NH 3.
4NH 3+5O 2→4NO+6H 2O (9)
A vehicular manufacturer has reported the observation to this phenomenon in SAE paper2009-01-0627, and its name is called " Impact and Prevention of Ultra-Low Contamination of Platinum Group Metals on SCR catalysts Due to DOC Design " and has comprised that the Fe/ zeolite scr catalysts that series connection is positioned at after four suppliers' the DOC of platinum group metal (PGM) is contacting the NO of 16 hours with flow model waste gas at 850 ℃ xactivity of conversion comparing data in time.The data that present show that being arranged on total PGM is 70g ft -320Pt:Pd DOC after the NO of Fe/ zeolite scr catalysts xactivity of conversion has disadvantageous change in the time of higher evaluation temperature compared with lower evaluation temperature, and this is to be polluted and caused by Pt.Also having tested total PGM is 105g ft -3two kinds of 2Pt:Pd DOC from different suppliers.In the first 2Pt:Pd DOC, similar to the degree that 20Pt:Pd DOC is tested to the influence degree of SCR catalytic activity, and the 2Pt:Pd DOC testing for the second, SCR catalyst activity pollution level is lower, but the NO of reduction is compared or demonstrated to the second 2Pt:Pd DOC and blank sample (without DOC, being only exposed substrate) xactivity of conversion.Author concludes, demonstrates the NO more relaxing xthe supplier of the second 2Pt:Pd DOC that conversion ratio reduces is using 35g ft -3pd stablizes existing 70g ft -3pt aspect is more successful.150g ft -3only confirm that containing the DOC of Pd the SCR that compares downstream with blank sample does not affect.SAE2009-01-0627 author's early stage work is disclosed in SAE paper no.2008-01-2488.
Vehicular manufacturer has started requirement applicant/assignee means of seeking and has solved the problem that the PGM of relative low content volatilizees from the assembly of SCR catalyst upstream.Wish that very much R & D Strategy prevents that this PGM is in the high temperature movement of SCR catalyst downstream.The inventor has has researched and developed multiple strategies to meet this demand.
US7,576,031 disclose the Pt-Pd diesel oxidation catalyst with CO/HC igniting (light-off) and HC memory function.Especially, this diesel oxidation catalyst is containing washcoat composition, and this washcoat composition comprises two different washcoat.First (or on) washcoat comprises high surface area support material, one or more hydrocarbon storage component and contains platinum (Pt) and the noble metal catalyst of palladium (Pd).The noble metal catalyst that second (or under) washcoat comprises high surface area support material and contains platinum (Pt) and palladium (Pd), wherein this carrier material is the carrier material that does not basically contain silica, and hydrocarbonaceous storage component not.
US7,576, in 031, disclosed two-layer diesel oxidation catalyst has two kinds of remarkable different Pt:Pd weight ratios each other, and wherein the Pt:Pd weight ratio in ground floor (first or upper washcoat) is greater than the Pt:Pd weight ratio in the second layer (second or lower washcoat).For example, first or upper washcoat can comprise at least Pt:Pd weight ratio of 2:1.Also exemplified from least about 2:1 to about 10:1, Pt:Pd weight ratio from about 3:1 to about 5:1 or from about 3:1 to about 4:1.According to explanation, first or on to use the Pt of high-load in washcoat be important, thereby in keeping Metal Phase more stable for sintering, strengthen sulphur tolerance.First and upper washcoat comprise hydrocarbon (HC) storage component (for example zeolite), to store HC driving in the cold start-up process in period in cycle.After catalyst warms up, this hydrocarbon (HC) storage component will discharge the HC of storage, and it transforms subsequently on catalyst.Continue to have described that hydrocarbon (HC) storage component (for example zeolite) is mixed in the layer with higher Pt:Pd weight ratio is important, effective conversion of the alkane being discharged to guarantee.
US7, second or lower floor of disclosed diesel oxidation catalyst comprises lower Pt:Pd weight ratio in 576,031, replaces the Pt of maximum with Pd for maximum cost savings reason.This second or lower washcoat there is the Pt:Pd weight ratio that is less than about 2:1.And, exemplify from being less than about 2:1 to about 1:2 or from being less than the Pt:Pd weight ratio of about 2:1 to about 1.4:1 (7:5).But preferably minimum ratio is 1.4:1 (7:5), light a fire active with enough CO/ alkene after guaranteeing heat ageing.
Summary of the invention
Therefore, research and development, for the oxidation catalyst of internal combustion engine (particularly compression-ignition engine), can be removed continuously and effectively thus SOF, HC and CO and preferably wherein can also greatly avoid sulfur poisoning, have become now the task of top priority.In recent years, the demand that produced is researched and developed the minimizing consumption of expensive and rare noble metal up to now, has the catalyst of the disposal ability identical with existing exhaust gas cleaning catalyst simultaneously.
The difference that the inventor is surprised to find the amount (load capacity) of noble metal and hydrocarbon adsorbent in catalyst layer can produce favourable catalyst activity, especially for by the HC in exhaust and CO (particularly CO) being converted into water and carbon dioxide and they being processed.
In first aspect, the invention provides for the hydrocarbon (HC) of oxidation processes waste gas and the oxidation catalyst of carbon monoxide (CO), this oxidation catalyst comprises bearing basement and loads on the multiple catalyst layers in this bearing basement, wherein the plurality of catalyst layer comprises washcoat material, active metal and hydrocarbon adsorbent, and one of them catalyst layer is positioned at catalyst surface layer side, one or more other catalyst layers are positioned at than in the low side of a described catalyst layer, wherein:
(a) in a described catalyst layer, the amount of hydrocarbon adsorbent is greater than the amount of hydrocarbon adsorbent in described one or more other catalyst layers, and in a described catalyst layer, the concentration of active metal is equal to or less than the concentration of active metal in described one or more other catalyst layers; Or
(b) in a described catalyst layer, the amount of hydrocarbon adsorbent equals the amount of hydrocarbon adsorbent in described one or more other catalyst layers, and in a described catalyst layer, the concentration of active metal is less than the concentration of active metal in described one or more other catalyst layers.
By utilizing hydrocarbon (HC) absorption and memory function, oxidation catalyst of the present invention can even effectively be processed carbon monoxide (CO) in lower temperature.In the time of Exhaust temperature rise, the hydrocarbon of storage (HC) discharges, and because temperature is high, therefore becomes available this catalyst and carries out oxidation processes.Hydrocarbon adsorbent between the exhaust gas cleaning effect that catalyst of the present invention is favourable and layer is relevant with the distribution of active metal.It is believed that, by HC absorption and memory function being given to " catalyst layer " of exhaust gas catalyst side upper surface layer, suppress the blocking action of the CO oxidation reaction in " other catalyst layers " in the catalyst surface layer side to closing on substrate carrier, when the concentration of noble metal is low in " catalyst layer " in catalyst surface layer side, in the time that the hydrocarbon of absorption and storage is discharged, due to the partial oxidation of hydrocarbon, the generation of CO is suppressed.
Conventionally, the oxidation catalyst in a first aspect of the present invention is catalytic substrate material all in one piece, and bearing basement is substrate material all in one piece.This catalyst layer can be the first washcoat defined herein, and one of these other catalyst layers can be the second washcoat defined herein.
Therefore, a first aspect of the present invention further relates to the catalytic substrate material all in one piece for the hydrocarbon of oxidation processes waste gas (HC) and carbon monoxide (CO), this catalytic substrate material all in one piece comprises substrate material all in one piece, the first washcoat and the second washcoat, wherein the second washcoat is arranged in the layer on the first washcoat, wherein the first washcoat comprises and contains active metal and the carbon monoxide-olefin polymeric at least one carrier material of this active metal, the second washcoat comprises hydrocarbon adsorbent, wherein:
(a) in the second washcoat, the amount of hydrocarbon adsorbent is greater than the amount of hydrocarbon adsorbent in the first washcoat, and in the second washcoat, the concentration of active metal is equal to or less than the concentration of active metal in the first washcoat; Or
(b) in the second washcoat, the amount of hydrocarbon adsorbent equals the amount of hydrocarbon adsorbent in the first washcoat, and in the second washcoat, the concentration of active metal is less than the concentration of active metal in the second washcoat.
The inventor also finds, in the time that Pt:Pd weight ratio is equal to or greater than about 2:1, platinum also can occur from comprising volatilizing containing the catalyst of PGM of platinum and palladium in extreme temperature conditions.Also it is believed that being made up of platinum at PGM (platinum group metal) is in situation, also can observe the volatilization of platinum.The inventor has designed stratiform PGM carbon monoxide-olefin polymeric, for combining with downstream SCR catalyst, avoids like this or has reduced the problem of PGM (particularly Pt) from the Pt catalyst migration of the relative high capacity in upstream to downstream SCR catalyst.
A second aspect of the present invention provides the catalytic substrate material all in one piece for the treatment of the waste gas going out from fuel-sean engine exhaust, it is included in the oxidation catalyst on substrate material all in one piece, this catalytic substrate material all in one piece comprises the first washcoat (conventionally having length L) and the second washcoat, wherein the second washcoat is arranged in layer on the first washcoat (be generally length L at least some), wherein the first washcoat comprises and contains platinum and the carbon monoxide-olefin polymeric at least one carrier material of platinum, wherein the second washcoat comprises and contains platinum and palladium and the carbon monoxide-olefin polymeric at least one carrier material of platinum and palladium, wherein in the second washcoat, the weight ratio of platinum and palladium is≤2, for example 1.5:1 or about 1:1, for example≤1:1.The importance of a rear feature shows in certain embodiments: the inventor tests discovery by experience, and the similar catalyst that preferred Pt:Pd weight ratio volatile ratio Pt:Pd weight ratio is 4:1 is few.
A third aspect of the present invention provides the gas extraction system for fuel-sean internal combustion engine, and this system comprises according to the first catalytic substrate material all in one piece of the present invention, particularly according to the catalytic substrate material all in one piece of a second aspect of the present invention.
A fourth aspect of the present invention provides the fuel-sean internal combustion engine comprising according to gas extraction system of the present invention, especially for vehicle.This fuel-sean internal combustion engine can be positive ignition (for example spark ignition) engine, it for example, moves with the blend of vapour Water Oil Or Gas and other components (ethanol) conventionally, but preferably compression ignition (for example diesel-type engine).Fuel-sean internal combustion engine comprises homogeneous charge compression-ignition (HCCI) engine, provides power by the fuel such as gasoline or diesel fuel.
A fifth aspect of the present invention provides and has reduced or prevent that in the gas extraction system of fuel-sean internal combustion engine, SCR (SCR) catalyst becomes the method for platinosis, this platinum can evaporate from comprising the first washcoat (conventionally having length L) that contains platinum and at least one carbon monoxide-olefin polymeric for the carrier material of platinum in the time that the carbon monoxide-olefin polymeric that comprises platinum is exposed to relatively extreme condition, this first washcoat is positioned on the substrate material all in one piece of SCR catalyst upstream, this relatively extreme condition comprises higher temperature, the method comprises the platinum of volatilization is captured in to the second washcoat that is arranged in the layer (be generally length L at least some) on the first washcoat, this second washcoat comprises and contains platinum and palladium and the carbon monoxide-olefin polymeric at least one carrier material of platinum and palladium, wherein in the second washcoat, the weight ratio of platinum and palladium is≤2.
A sixth aspect of the present invention provides for example, gas extraction system for internal combustion engine (particularly compression-ignition engine, Diesel engine), and this system comprises according to the oxidation catalyst of a first aspect of the present invention or catalytic substrate material all in one piece.
A seventh aspect of the present invention provides the internal combustion engine comprising according to the gas extraction system of a sixth aspect of the present invention, especially for vehicle.This internal combustion engine can be positive ignition (for example spark ignition) engine, and it uses the blend operation of vapour Water Oil Or Gas and other components (for example ethanol) conventionally, but preferably compression ignition (for example diesel-type engine).
A seventh aspect of the present invention provides the vehicle comprising according to engine of the present invention.
Accompanying drawing summary
Fig. 1 is the schematic diagram for the laboratory reaction device of the platinum pollution on the Fe/ β of Cu/CHA zeolite scr catalysts or embodiment 6 zeolite scr catalysts of test implementation example 2.
Fig. 2 be two kinds of comparisons through aging SCR catalyst core at 500 ℃ of (α 0.8, i.e. NH 3: NO x) NO xthe block diagram of activity of conversion, two kinds all aging in the laboratory scale gas extraction system shown in Fig. 1 of the diesel oxidation catalyst core product that comprise comparative example 6 and embodiment 4, it heats 2 hours at 900 ℃ in tube furnace in the synthetic waste gas flowing, and the Cu/CHA zeolite scr catalysts core that remains on 300 ℃ is positioned at downstream;
Fig. 3 is the NO that has drawn fresh Fe/ β zeolite scr catalysts xactivity of conversion is as the figure of the function of temperature, and the activity of crossing the Fe/ β zeolite scr catalysts of aging mistake in the laboratory scale gas extraction system shown in Fig. 1 of filter core with the catalysis cigarette ash that comprises comparative example 7 and embodiment 7 and 8 compares.
Fig. 4 is the NO that shows two kinds of different Cu/CHA SCR catalyst xthe block diagram of activity of conversion, two kinds are all carried out agingly in the diesel oxidation catalyst downstream of embodiment 10, and have total Pt:Pd weight ratio of 4:1 and 2:1 with respect to the control sample of SCR catalyst.
Fig. 5 is the schematic diagram according to the gas extraction system of the first most preferred embodiment according to a third aspect of the present invention.
Fig. 6 is the schematic diagram according to the gas extraction system of the second most preferred embodiment according to a third aspect of the present invention.
Fig. 7 is the schematic diagram according to the gas extraction system of the 3rd most preferred embodiment according to a third aspect of the present invention.
Detailed Description Of The Invention
Oxidation catalyst and catalytic substrate material all in one piece
Conventionally, each catalyst layer or washcoat have the average thickness of 25-200 μ m, are 50-150 μ m especially, are more particularly that (for example 100 μ m) for 75-125 μ m.Layer thickness can use probe-microanalyser to measure.
The average thickness of each catalyst layer or washcoat can be identical or different.In one embodiment of the present invention, the average thickness an of catalyst layer (for example the second washcoat) and at least one other catalyst layer (for example the first washcoat) is roughly the same.
Oxidation catalyst of the present invention or catalytic substrate material all in one piece comprise multiple catalyst layers or washcoat.Conventionally, oxidation catalyst or catalytic substrate material all in one piece are made up of 2,3,4 or 5 catalyst layers or washcoat.Preferential oxidation catalyst or catalytic substrate material all in one piece are made up of two catalyst layers or washcoat.In the context of a first aspect of the present invention, " catalyst layer " and one or more " other catalyst layers " is in multiple catalyst layers, the present invention is positioned at " catalyst layer " in multiple catalyst layers in catalyst surface layer side, and " other catalyst layers " is positioned to a side (in bearing basement side) lower than " catalyst layer ".
Conventionally, the component of adsorbed hydrocarbons (for example hydrocarbon adsorbent) has the high-specific surface area for contacting with waste gas.Conventionally, hydrocarbon adsorbent has 50-1500m 2the specific area of/g, preferably 200-1000m 2/ g, more preferably 200-900m 2/ g.Specific area is used nitrogen as absorption-desorption eudiometry by BET nitrogen adsorption method.
Conventionally, hydrocarbon adsorbent is selected from zeolite, silica, aluminium oxide, titanium oxide, zirconia, magnesia, calcium oxide, cerium oxide, niobium oxide, activated coke, porous graphite and the combination of two or more thereof.Preferably, hydrocarbon adsorbent is zeolite.The example of applicable zeolite comprises: natural zeolite, for example analcime, chabasie, erionite, sodalite, modenite, heulandite, foresite and laumontite; And synthetic zeolite, for example A type zeolite, y-type zeolite, X-type zeolite, zeolite L, erionite, modenite, β zeolite and ZSM-5.
The ratio of the content in a described catalyst layer or the second washcoat in the content of hydrocarbon adsorbent and described one or more other catalyst layers or the first washcoat is generally 10:1-1.1:1, be 7.5:1-1.2:1 especially, be more particularly 5:1-1.3:1, being even more particularly 4:1-1.4:1, is more particularly still 3:1-1.5:1.
Conventionally, this catalyst layer or the second washcoat have 0.05-3.00g in -3the concentration of hydrocarbon adsorbent, be 0.10-2.00g in especially -3, be more particularly 0.25-0.75g in -3.In one or whole layers, the amount of hydrocarbon adsorbent is relevant with the trapping capacity of oxidation catalyst or catalytic substrate material all in one piece.
In " catalyst layer " amount of hydrocarbon adsorbent be characterized as the amount that is greater than hydrocarbon adsorbent in " other catalyst layers ", and in " catalyst layer ", the concentration that exists of aforementioned active metal is less than the concentration that exists of aforementioned active metal in " other catalyst layers "; And catalyst layer can be stacked as to be made, and " catalyst layer " is adjacent with " other catalyst layers ", and catalyst layer (or other layer, it is the layer with identical or different composition) in the middle of can getting involved betwixt.In addition, the present invention selects two catalyst layers that are applicable to arbitrarily and locates them to make " catalyst layer " to be positioned at catalyst surface layer side and " other catalyst layers " is positioned at a side lower than aforementioned catalyst layer (bearing basement side) in multiple catalyst layers; Wherein, if defined " catalyst layer ", so other is just defined as " other catalyst layers " automatically.
Catalyst layer or the second washcoat have the concentration of the hydrocarbon adsorbent of the 10-50wt% of this layer or washcoat conventionally, are 15-40wt% especially, are more particularly 20-30wt%.
Active metal is as the catalytic active component of oxidation catalyst or catalytic substrate material all in one piece.Active metal is noble metal, base metal or platinum group metal (PGM).
The example of applicable noble metal comprises platinum, palladium, rhodium, ruthenium, iridium, osmium, Jin Heyin.In the time that active metal is noble metal, so preferably this active metal is platinum, palladium or gold.Noble metal can use separately or as the mixture of two or more, the mixture of the mixture of for example platinum and palladium or platinum, palladium and gold.
The example of base metal comprises nickel, copper, manganese, iron, cobalt and zinc.In the time that active metal is base metal, so preferably this active metal is nickel, copper, manganese or iron.Base metal also can use separately or as the mixture of two or more.
Active metal in this catalyst layer or the second washcoat can with one or more other catalyst layers or the first washcoat in active metal identical or different.
Preferably active metal is platinum group metal.More preferably active metal is platinum, palladium or its mixture.
In the time that this catalyst layer or the second washcoat and these one or more other catalyst layers or the first washcoat all exist active metal in the two, active metal can be identical or different so.
Conventionally, the ratio of the concentration in a described catalyst layer (or second washcoat) for example, in concentration and described one or more other catalyst layers (or first washcoat) of active metal (platinum group metal (PGM)) is 1:50-1:1.1, be 1:35-1:1.2 especially, be more particularly 1:20-1:1.3, being even more particularly 1:15-1:1.4, is more particularly still 1:10-1:1.5 (for example 1:5-1:1.5).
Conventionally, these one or more other catalyst layers (or first washcoat) have 0.05-3.5g in -3active metal (for example PGM) concentration, be 0.1-1.5g in especially -3, be more particularly 0.25-0.75g in -3, for example 0.1-0.75g in -3.The amount of active metal has determined the quantity of the active sites that can be used for catalysis.
Conventionally, these one or more other catalyst layers (or first washcoat) have the concentration of the active metal (for example PGM) of 0.05-7.5wt%, are 0.5-5wt% especially, are more particularly 1-3wt%.
This catalyst layer (or second washcoat) has the concentration of the active metal (for example PGM) of 0.01-5wt% conventionally, is 0.05-0.5wt% especially, is more particularly 0.1-0.3wt%.
In one embodiment of the present invention, in these one or more other catalyst layers or the first washcoat, there is no hydrocarbon adsorbent.Relevant to a first aspect of the present invention, in the time there is no hydrocarbon adsorbent in these one or more other catalyst layers or the first washcoat, in this catalyst layer or the second washcoat, can there is no active metal so, or active metal is so that concentration or ratio exist as defined above.
In the time all there is hydrocarbon adsorbent in this catalyst layer or the second washcoat and these one or more catalyst layers or the first washcoat, hydrocarbon adsorbent can be identical or different so.Preferably, the hydrocarbon adsorbent in each catalyst layer or washcoat is identical.
In the time that the amount of the hydrocarbon adsorbent in a described catalyst layer or the second washcoat is greater than the amount of hydrocarbon adsorbent in described one or more other catalyst layers or the first washcoat, in this catalyst layer or the second washcoat, the weight of catalyst is less than or approximates the weight of catalyst in these one or more catalyst layers or the first washcoat conventionally so.
Conventionally, washcoat material is the carrier material for active metal.This carrier material is for example: metal oxide, is selected from oxide, its composite oxides and the mixture of two or more thereof of Mg, Si, Ca, Sr, Ba, Al, Ga, In, Sn, transition metal, lanthanide series.Preferably, this carrier material is selected from SiO 2, Al 2o 3, CeO 2and TiO 2or there is SiO 2, Al 2o 3, CeO 2or TiO 2as the composite oxides of its main component.
Oxidation catalyst or catalytic substrate material all in one piece can further comprise co-catalyst, for example cerium oxide, zirconia or titanium oxide.
Conventionally bearing basement supported catalyst (such as active metal, hydrocarbon adsorbent, washcoat material, co-catalyst etc.).This bearing basement can be can be by do not reduce the efficiency of combustion of engine with the problem such as the pressure loss and have any bearing basement of durability and reliability simultaneously.
Conventionally, bearing basement is pottery or metal material.For example, it can be the form of tubulose, fiber or particle.The example of applicable bearing basement comprises substrate, the substrate of foam build, the substrate of cross-current ejector half, the substrate of metal mesh type, the substrate of metal porous build and the substrate of ceramic particle type of substrate, layered fibre or the knitted fabric type of substrate, the monolithic, honeycomb SiC type of monolithic, honeycomb cordierite type.This bearing basement can be selected from cordierite (SiO 2-Al 2o 3-MgO), carborundum (SiC), Fe-Cr-Al alloy, Ni-Cr-Al alloy and stainless steel alloy.
Preferably, bearing basement is substrate material all in one piece.
Conventionally, in the present invention's (particularly a second aspect of the present invention), substrate material all in one piece used can be the filtration substrate material all in one piece with inlet surface and exit surface, and wherein inlet surface and exit surface are separated by cell structure.Particularly preferred filtration substrate material all in one piece is wall-flow filter.But in particularly preferred embodiments, this substrate material all in one piece is flow type substrate material all in one piece.
At least one carrier material (being washcoat material) of the first washcoat or the second washcoat can comprise the freely metal oxide of the following group forming of choosing: the Ceria-zirconia mixed oxide of zirconia, cerium oxide, titanium oxide and the optional stabilisation of the aluminium oxide of optional stabilisation, amorphous silica-aluminium oxide, optional stabilisation or molecular sieve or its mixture of two or more arbitrarily.
The first washcoat can be extended the whole length substantially of passage in substrate material all in one piece.In the first special embodiment, the second washcoat covers the first washcoat substantially.In the second embodiment, the second washcoat is arranged in the length of downstream end of substrate material all in one piece substantially uniformly in district, this district is limited by the port of export of substrate material all in one piece itself in downstream, and is limited by certain point shorter than the whole length of the first washcoat at upstream extremity.,, in the second embodiment, the second washcoat does not cover the whole of the first washcoat.The method of preparing the layered coating of different length is as known in the art, for example, referring to WO99/47260 with described in herein.
In any of first, second, and third most preferred embodiment according to catalytic substrate material all in one piece of the present invention, the first washcoat can comprise the 25-75wt% of total platinum group metal of the existence of the first washcoat and the second washcoat total, for example its 35-65wt%., the second washcoat can comprise the 75-25wt% of total platinum group metal of the existence of the first washcoat and the second washcoat total, for example 65-35wt%.Inventor's discovery, the PGM load capacity in washcoat is not broadly depended in PGM volatilization, and more depends on the weight ratio of Pt:Pd as above.But, preferably more amount in total PGM amount is placed in the second washcoat, because it more easily carries out mass transfer.Therefore, preferably in the second washcoat, there is the >50wt% of total platinum group metal of the existence of the first washcoat and the second washcoat total.
Relate to the distribution of total platinum group metal weight between the first washcoat and the second washcoat Catalyst Design aspect be the first washcoat and the second washcoat washcoat load capacity in separately.In embodiments, the first washcoat and the second washcoat washcoat load capacity in is separately independently selected from 0.1-3.5g in -3scope, for example 0.5-2.5g in -3, for example>=1.5g in -3,>=2.0g in -3or≤2.0g in -3.For for example NO xadsorber catalyst, preferably higher load capacity.But, by using than washcoat load capacity lower in the first washcoat, can in the first washcoat of easier mass transfer, prepare more not " easily contacting " PGM in the second washcoat., in embodiments, the washcoat load capacity in the first washcoat is greater than the washcoat load capacity in the second washcoat.
In a second aspect of the present invention, at least one carrier material (or washcoat) can comprise one or more molecular sieves, for example aluminosilicate zeolite.The Main Function of the molecular sieve in the catalytic substrate of a first aspect of the present invention is for by store hydrocarbon after cold start-up or in the cold phase process of work period, and when relevant platinum metal catalysts component discharges the hydrocarbon of storage in higher temperature when conversion has more activity to HC, and on the work period, improve hydrocarbon conversion rate.For example, referring to EP0830201.Molecular sieve be generally used for light diesel vehicle according in carbon monoxide-olefin polymeric of the present invention, and it is rarely used in the carbon monoxide-olefin polymeric of heavy-duty diesel oil application, does not conventionally need hydrocarbon trapping function because the EGT in heavy duty diesel engine means.But the in the situation that of there is molecular sieve according to catalytic substrate material all in one piece of the present invention, very preferably at least one in the first washcoat and the second washcoat comprises molecular sieve.More preferably, the first washcoat and the second washcoat all comprise molecular sieve.
But, molecular sieve (for example aluminosilicate zeolite) is not the particularly preferred carrier material for platinum group metal, because it is mainly silica, silica: aluminium oxide is than relatively high especially molecular sieve, this is conducive to improve its heat resistance: it in ageing process, thermal degradation may occur, the structure of molecular sieve may be caved in and/or PGM possibility sintering, produce lower decentralization and therefore reduce HC and/or CO activity of conversion.Therefore, in preferred embodiments, the first washcoat and the second washcoat comprise each washcoat≤molecular sieve of 30wt% (as≤25wt% ,≤20wt%, for example≤15wt%).Remaining at least one carrier material of the first washcoat or the second washcoat can comprise the freely metal oxide of the following group forming of choosing: optionally the Ceria-zirconia mixture oxide of the zirconia of the aluminium oxide of stabilisation, amorphous silica-aluminium oxide, optional stabilisation, cerium oxide, titanium oxide and optional stabilisation and the arbitrarily mixture of two or more.
As the preferred molecular sieve of carrier material/hydrocarbon adsorbent be: mesopore zeolite, preferably aluminosilicate zeolite, has those of maximum loop size of eight tetrahedron atoms; And large pore zeolite (maximum ten tetrahedron atoms), preferably aluminosilicate zeolite, comprise natural or synthetic zeolite, for example faujasite, clinoptilolite, modenite, silicalite, ferrierite, X zeolite, zeolite Y, overstable zeolite Y, ZSM-5 zeolite, ZSM-12 zeolite, SSZ-3 zeolite, SAPO-5 zeolite, christianite or β zeolite, preferably ZSM-5, β and Y zeolite.Preferred zeolite adsorption agent material has high silicon dioxide: aluminium oxide ratio, and for improving hydrothermal stability.This zeolite can have the silica/alumina mole ratio at least about 25/1, and preferably at least about 50/1, useful scope is about 25/1-1000/1,50/1-500/1 and about 25/1-100/1,25/1-300/1, about 100/1-250/1.
Oxidation catalyst in the catalytic substrate material all in one piece of the oxidation catalyst of a first aspect of the present invention or a second aspect of the present invention can be diesel oxidation catalyst or NOx adsorbent catalyst, has the effect of describing in the background of invention on herein.Compared with oxidation catalyst, the alkaline-earth metal that NAC comprises significant quantity and/or alkali metal.This NAC also comprises the mixed oxide of cerium oxide or oxidation-containing cerium conventionally, the mixed oxide of for example cerium and zirconium, and this mixed oxide optionally further comprises one or more other lanthanide series or rare earth elements.
The preparation method who comprises the catalytic substrate material all in one piece of individual layer washcoat and rebuilding (washcoat is on another washcoat) is as known in the art, and comprise WO99/47260, comprise the following steps: (a) will hold instrument and be placed in the top first end of substrate material all in one piece; (b) described in being added, the first washcoat component of scheduled volume holds in instrument, with (b) after elder generation (a) or first order of (a) after (b); (c) by implementing pressure or vacuum, the first washcoat component is drawn at least a portion of substrate material all in one piece, and almost all remaining in this substrate material all in one piece described amount.In the first step, can be by dry from applying the coating that first end obtains, and the substrate material all in one piece of drying can be turned over to turnback, top the second end for substrate material all in one piece also can carry out identical operation, there is no the overlapping of layer between the applying of the first and second ends from this substrate material all in one piece.Then obtained coating product is dry, then calcining.Repeat this technique by the second washcoat component, to provide according to catalysis of the present invention (bilayer) substrate material all in one piece.
Of the present invention first or second aspect in the preferably wall-flow filter of filtration substrate material all in one piece that uses, comprise the ceramic porous filtration substrate of the multiple access roades that are arranged in parallel with multiple exit passageways, wherein each access road and each exit passageway are partly limited by the ceramic wall of cell structure, wherein each access road and exit passageway alternately separate by the ceramic wall of cell structure, and vice versa.In other words, wall-flow filter is cellular layout, define multiple upstream extremity stop up first passages and multiple upstream extremity do not stop up but downstream stop up second channel.Stop up in downstream with laterally adjacent passage with first passage is vertical.In the time observing from arbitrary end, the alternately obstruction of passage and the end of opening present the outward appearance of chessboard.
Catalytic filter (preferably wall-flow filter) can use disclosed method in WO2011/080525 to apply.That is, apply the method for the cellular monolith substrates that comprises multiple passages, the plurality of passage has the liquid that comprises catalytic component, and the method comprises the following steps: (i) cellular monolith substrates is kept to vertical substantially; (ii) this liquid of predetermined is introduced in this substrate via the openend of the passage of this substrate lower end; (iii) hydraulic seal of introducing is remained in this substrate; (iv) substrate that comprises kept liquid is inverted; (v) in the inverted lower end of this substrate, the openend of the passage to this substrate applies vacuum, to extract this liquid along the passage of this substrate.Carbon monoxide-olefin polymeric can be coated in filter passage from first end, then can be dried the filter through applying.Use the method can use for example vacuum strength, vacuum time, washcoat viscosity, washcoat solid, coating particles or aggregation size and surface tension to control; so that catalyst is mainly coated in inlet surface, and be optionally coated in the cell structure that approaches inlet surface.Alternatively, washcoat component can be ground to certain size (for example D90<5 μ m) so that the loose structure (referring to WO2005/016497) of its " infiltration " filter.The SCR catalyst of the second substrate material all in one piece can comprise filtration substrate material all in one piece, preferably wall-flow type material all in one piece or flow type substrate material all in one piece.Flow type substrate material all in one piece can be to extrude SCR catalyst or activation is coated to the SCR catalyst on inertia substrate material all in one piece.Can also prepare wall-flow filter (referring to WO2009/093071 and WO2011/092521) by extruding SCR catalyst.SCR catalyst can select the freely group with at least one lower formation: Cu, Hf, La, Au, In, V, lanthanide series and group VIII transition metal (for example Fe), it loads on refractory oxides or molecular sieve.Applicable refractory oxides comprises Al 2o 3, TiO 2, CeO 2, SiO 2, ZrO 2with comprise its two or more mixed oxide.Non-zeolite catalysts can also comprise tungsten oxide, for example V 2o 5/ WO 3/ TiO 2.The group that the special preferable alloy of being concerned about selects free Ce, Fe and Cu to form.Can carry out ion-exchange with any above-mentioned metal pair molecular sieve.
In specific embodiments, this at least one molecular sieve is aluminosilicate zeolite or SAPO.This at least one molecular sieve can be for example aperture, mesopore or large pore molecular sieve." small pore molecular sieve " herein represents the molecular sieve of the maximum loop size that comprises 8 tetrahedron atoms, for example CHA; " mesoporous molecular sieve " herein represents the molecular sieve of the maximum loop size that comprises 10 tetrahedron atoms, for example ZSM-5; " large pore molecular sieve " herein represents the molecular sieve of the maximum loop size that comprises 12 tetrahedron atoms, for example β zeolite.Small pore molecular sieve is potential favourable for using in SCR catalyst, for example, referring to WO2008/132452.Comprise according to molecular sieve used in SCR catalyst of the present invention one or more metals that mix in framework of molecular sieve, for example Fe at the β of " in skeleton " zeolite and Cu the CHA at " in skeleton ".
Can be used for the freely following group forming of concrete molecular screening in the present invention: AEI, ZSM-5, ZSM-20, ERI (comprising ZSM-34), modenite, ferrierite, BEA (comprising β), Y, CHA, LEV (comprising Nu-3), MCM-22 and EU-1, at present preferred CHA molecular sieve, particularly for example combines by ion-exchange with the Cu as auxiliary agent.
In the embodiment of a first aspect of the present invention, in this catalyst layer or the second washcoat, there is no active metal, for example PGM.In the time there is no active metal in these other catalyst layers or the second washcoat, in these one or more other catalyst layers or the first washcoat, can there is no hydrocarbon adsorbent so, or this hydrocarbon adsorbent can be so that concentration or ratio exist as defined above.
In the other embodiments of a first aspect of the present invention, the first washcoat comprises and contains platinum and at least one carbon monoxide-olefin polymeric for the carrier material of platinum, the second washcoat comprises and contains platinum and palladium and at least one carbon monoxide-olefin polymeric for the carrier material of platinum and palladium, wherein in the second washcoat, the weight ratio of platinum and palladium is≤2, for example 1.5:1 or about 1:1, for example≤1:1.
In the embodiment of a second aspect of the present invention, the amount of hydrocarbon adsorbent in the second washcoat (for example zeolite) is greater than the amount of hydrocarbon adsorbent in the first washcoat.Preferably, the concentration of active metal in the second base coating (for example platinum and palladium) is equal to or less than the concentration of active metal in the first base coating (for example platinum), preferably lower than.The amount of hydrocarbon adsorbent as above defines.
In the other embodiments of a second aspect of the present invention, the amount of hydrocarbon adsorbent in the second washcoat (for example zeolite) is identical with the amount of hydrocarbon adsorbent in the first washcoat.Preferably, in the second base coating the concentration of active metal (for example platinum and palladium) for example, lower than the concentration of active metal in the first base coating (platinum).
Gas extraction system
According to the 3rd and the 6th aspect, the inventor provides the gas extraction system for fuel-sean internal combustion engine, and this system comprises according to the first catalytic substrate material all in one piece of the present invention.
In preferred embodiments, gas extraction system according to the present invention's (particularly a third aspect of the present invention) comprises the second catalytic substrate material all in one piece, this the second catalytic substrate material all in one piece comprises SCR (SCR) catalyst, and this second catalytic substrate material all in one piece is positioned at the downstream of the first catalytic substrate material all in one piece.In preferred embodiments, the present invention's's (particularly a third aspect of the present invention) gas extraction system comprises injector, and it for injecting waste gas by nitrogenous reducing agent between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece.Alternatively (for example between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece, be not provided for, by the instrument of ammonia or its precursor (urea) injection), or except the instrument for injecting ammonia or its precursor, in another embodiment, provide engine management instrument for enrichment exhaust, so that pass through reductive NO on the carbon monoxide-olefin polymeric of the first catalytic substrate material all in one piece xoriginal position generates ammonia.
Nitrogenous reducing agent and precursor thereof for the present invention comprise herein those that mention relevant to background technology part above, for example ammonia and urea.
Combine with the diesel oil compression ignition engine of suitable design and management, the waste gas (comparing with normal fuel-sean operational mode the waste gas that comprises more substantial carbon monoxide and hydrocarbon) of enrichment contacts with the carbon monoxide-olefin polymeric of the first substrate material all in one piece.Component (cerium oxide or the Ceria-zirconia that for example promote with PGM) in NAC can promote water gas shift reaction, i.e. CO (g)+ H 2o (v)→ CO 2 (g)+ H 2 (g), give off H 2.For example, from the side reaction (Ba (NO of the footnote of reaction recited above (3) and (4) herein 3) 2+ 8H 2→ BaO+2NH 3+ 5H 2o) known, can original position generate NH 3, and stored for the NO on the SCR catalyst of downstream xreduction.
In the first most preferred embodiment, the present invention's's (particularly a third aspect of the present invention) gas extraction system comprises the 3rd catalytic substrate material all in one piece, wherein the substrate material all in one piece of the first catalytic substrate material all in one piece is flow type substrate material all in one piece, wherein the 3rd catalytic substrate material all in one piece is the filtration substrate material all in one piece with inlet surface and exit surface, and wherein inlet surface and exit surface are separated by cell structure, the 3rd catalytic substrate material all in one piece comprises oxidation catalyst and between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece, and preferably at the first catalytic substrate material all in one piece and for nitrogenous reducing agent is injected between any injector of waste gas between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece.
In the second most preferred embodiment, the second catalytic substrate material all in one piece of the present invention's's (particularly a third aspect of the present invention) gas extraction system is the filtration substrate material all in one piece with inlet surface and exit surface, and wherein inlet surface and exit surface are separated by cell structure.
In the 3rd most preferred embodiment, the present invention's's (particularly a third aspect of the present invention) gas extraction system comprises the 3rd substrate material all in one piece, wherein the 3rd substrate material all in one piece is the filtration substrate material all in one piece with inlet surface and exit surface, wherein inlet surface and exit surface are separated by cell structure, and the 3rd substrate material all in one piece is positioned at the downstream of the second catalytic substrate material all in one piece.In specific embodiments, the 3rd substrate material all in one piece comprises oxidation catalyst., in one embodiment, the 3rd substrate material all in one piece is not containing any coating.
In first, second, and third most preferred embodiment of the present invention's's (particularly a third aspect of the present invention) gas extraction system, preferably this filtration substrate material all in one piece or respectively to filter substrate material all in one piece be wall-flow filter.
Different from the first most preferred embodiment of the preferred effect of second and the 3rd the first catalytic substrate in most preferred embodiment of the present invention's (particularly a third aspect of the present invention).In most preferred embodiment, be and then the second substrate material all in one piece that comprises SCR catalyst at the catalytic substrate material all in one piece in the first catalytic substrate material all in one piece downstream second and the 3rd.In order to promote reaction (6), preferably the first catalytic substrate material all in one piece promotes NO oxidation, total but the NO that has also avoided PGM volatilization simultaneously and reduced thus with the backward SCR catalyst migration that is located immediately at downstream xactivity of conversion.
For this effect, the Pt:Pd weight ratio that preferably the first washcoat and the second washcoat amount to is >=2:1.Occur for fear of volatilization, the Pt:Pd weight ratio that preferably the first washcoat and the second washcoat amount to is≤10:1, for example≤8:1 ,≤6:1 or≤4:1.In specific embodiments, preferably the PGM in the first washcoat is only Pt, and it is not substantially containing palladium.In order to trap any platinum that may volatilize from the first washcoat, preferably the weight ratio of the platinum in the second washcoat and palladium is≤2, for example 1.5:1 or about 1:1, for example≤1:1.
" do not basically contain palladium " and be illustrated in relevant layers and do not have a mind to provide palladium.But, will be appreciated that, this material may be to be considered to immaterial a small amount of (be this material of <10%, <9%, <8%, <7%, <6%, <5%, <4%, <3%, <2% or even <1%) from the second washcoat migration or to be diffused into the first washcoat.
Aspect the of the present invention the 3rd and the 6th in first most preferred embodiment of the present invention of (preferably a third aspect of the present invention), the preferred effect of the first catalytic substrate and second and the 3rd most preferred embodiment different, because be provided with catalysis soot filter (the 3rd catalytic substrate material all in one piece) between the first substrate material all in one piece and the second substrate material all in one piece.Therefore, although can reduce or prevent PGM from the first catalytic substrate material all in one piece volatilization and move to subsequently the assembly in downstream, but there is the fact of catalysis soot filter in the downstream of the first substrate material all in one piece, this catalysis soot filter has preferably promoted the NO oxidation of the second substrate material all in one piece upstream that comprises SCR catalyst for promoting reaction (6), and therefore will comprise equally relatively high platinum content, can more effectively use in the first catalytic substrate material all in one piece downstream for the means of the PGM that traps volatilization.For example; the means that are used for the PGM that traps volatilization can be applied to the design aspect of catalysis soot filter, for example, protection bed (a guard bed) can be set between catalysis soot filter and the second catalytic substrate material all in one piece or in the inlet region of the second catalytic substrate material all in one piece self.These means are disclosed in applicant/assignee's homologous series application (sister applications): denomination of invention is " Catalysed Substrate Monolith "; " Exhaust System for a Lean Burn IC Engine comprising a PGM Component and a SCR Catalyst " and " Exhaust System for a Lean-Burn Internal Combustion Engine including SCR Catalyst ", submit to Ref. No. 70050,70051 and 70053 respectively.
Therefore, aspect the of the present invention the 3rd and the 6th in the situation of first most preferred embodiment of (particularly a third aspect of the present invention), the preferred effect of the first catalytic substrate material all in one piece is oxidizing carbon monoxide and unburned hydrocarbon (volatility organic moiety (VOF), also referred to as solvable organic moiety (SOF)), unnecessary NO is oxidized to NO 2to promote reaction (6).
Preferably, aspect the of the present invention the 3rd and the 6th in first most preferred embodiment of (particularly a third aspect of the present invention) in catalytic substrate material all in one piece used, the second washcoat comprises platinum and palladium, and the first washcoat comprises Pt:Pd weight ratio higher than the platinum in the second washcoat and palladium.That is, in the situation of the platinum in the second washcoat and weight ratio≤2 of palladium (for example, as 1.5:1 or about 1:1 ,≤1:1), this weight ratio in the first washcoat preferably >=1:2, most preferably from about 2:1.In specific embodiments, the Pt:Pd weight ratio that the first washcoat and the second washcoat amount to is >=1:1.
Fig. 5 is the schematic diagram according to the gas extraction system 10 of second most preferred embodiment of a third aspect of the present invention, and it is comprising according to being from upstream to being disposed in order of downstream: according to flow type substrate material all in one piece 2 of the present invention, it is coated with two-layer DOC composition; Downstream catalytic wall-flow filter substrate material all in one piece 4, its access road 100% on be coated with 5g ft -3load on the platinum in particulate alumina, and its exit passageway total length 35% on be coated with 1.75g ft -3load on the palladium in particulate alumina; Ammonia source 6, it comprises the injector for ammonia precursor urea; With flow type substrate material all in one piece 8, it is coated with Fe/ β SCR catalyst.Each substrate material all in one piece 2,4,8 is arranged in the canister or " tank " that comprise cone-shaped diffuser, and connects by a series of cross-sectional areas pipeline 3 less than the cross-sectional area of arbitrary substrate material all in one piece 2,4,8.Cone-shaped diffuser is scattered for the waste gas streams of the shell that will enter " canned " substrate material all in one piece, basic across " face " before each substrate material all in one piece whole on the whole to make waste gas.The waste gas that leaves substrate material all in one piece 8 is discharged in atmosphere at " tail pipe " 5 places.
Be coated with the flow type substrate material all in one piece 2 of double-deck DOC through designing to promote hydrocarbon, carbon monoxide and nitric oxide production oxidation, and in top layer, there is the Pt:Pd weight ratio of 2:1 and total Pt:Pd weight ratio of 6:1.Catalysis wall-flow type substrate material all in one piece 4 is described in denomination of invention that applicant/assignee submits to take Ref. No. 70050 on the date identical with the application in the homologous series patent application of " Catalysed Substrate Monolith ", the inventor of this invention finds, the palladium arranging in the downstream of the exit passageway of wall-flow filter can reduce or prevent that the platinum for example, volatilizing from the upstream access road of this wall-flow filter and/or the substrate material all in one piece (DOC of this wall-flow filter upstream) that comprises catalyst made from platonic from leading to SCR catalyst downstream, poison thus the NO on SCR catalyst xtransform, this may be by the Pt volatilizing and palldium alloy are realized.Similarly, total Pt:Pd weight ratio of double-deck DOC can be relatively high, and do not worry platinum from DOC volatilization and directly lead to SCR catalyst.But, to the second washcoat≤restriction of 2:1 has limited as far as possible may be from the amount of the platinum of DOC volatilization.
With reference to Fig. 6, show according to the gas extraction system 20 of second most preferred embodiment of a third aspect of the present invention, comprise according to the sequential order that is from upstream to downstream: circulation substrate material all in one piece 22, it is evenly coated with stratiform NAC composition; With downstream wall flow filter substrate material all in one piece 24, on its access road and exit passageway, be coated with CuCHA SCR catalyst.Each substrate material all in one piece 22,24 is arranged in the canister or " tank " that comprise cone-shaped diffuser, and connects by a series of cross-sectional areas pipeline 3 less than the cross-sectional area of arbitrary substrate material all in one piece 22,24.
The diesel oil compression ignition engine (upstream of substrate material all in one piece with suitable design and management, not shown) combine, the waste gas (comparing with normal fuel-sean operational mode the waste gas that comprises more substantial carbon monoxide and hydrocarbon) of enrichment contacts with NAC.Component (cerium oxide or the Ceria-zirconia that for example promote with PGM) in NAC can promote water gas shift reaction, i.e. CO (g)+ H 2o (v)→ CO 2 (g)+ H 2 (g), give off H 2.For example, from the side reaction (Ba (NO of the footnote of reaction recited above (3) and (4) herein 3) 2+ 8H 2→ BaO+2NH 3+ 5H 2o) known, can original position generate NH 3, and stored for the NO on the SCR catalyst of downstream wall streaming substrate material all in one piece 24 xreduction.The waste gas that leaves substrate material all in one piece 24 is discharged in atmosphere at " tail pipe " 5 places.The upper layer packets of stratiform NAC composition is containing weight ratio be 2:1 platinum and palladium, but total Pt:Pd weight ratio in NAC composition in its entirety is 4:1, to promote the NO oxidation of SCR catalyst upstream.
Fig. 7 is according to the schematic diagram of the gas extraction system 30 of the 3rd most preferred embodiment of a third aspect of the present invention, comprises according to the sequential order that is from upstream to downstream: circulation substrate material all in one piece 32, and it is evenly coated with double-deck DOC composition; Ammonia source 6, it comprises the injector for ammonia precursor urea; Downstream flow type monolith substrates 34, it is coated with CuCHA SCR catalyst; With the downstream catalytic soot filter based on wall-flow filter substrate 36.Each substrate material all in one piece 32,34,36 is arranged in the canister or " tank " that comprise cone-shaped diffuser, and connects by a series of cross-sectional areas pipeline 3 less than the cross-sectional area of arbitrary substrate material all in one piece 32,34,36.
In this embodiment, the flow type substrate material all in one piece 34 that is coated with SCR catalyst is communicated with the direct fluid of flow type substrate material all in one piece 32 that comprises DOC.In order to reduce or to prevent that platinum group metal is from DOC volatilization and to SCR catalyst migration, this bilayer DOC composition comprises platinum and palladium through design with the Pt:Pd weight ratio with 2:1 in the second washcoat.In order to promote NO oxidation to promote thus reaction (1) and (6), total Pt:Pd weight ratio is 4:1.
As explained above herein, the system of Fig. 7 is to arrange for the optimum decision system of heavy-duty diesel oil, because important Consideration is to realize as far as possible rapidly the NO in gas extraction system after vehicle motor starts xtransform, for example, to make (i) that the precursor of nitrogenous reducing agent (ammonia) is injected/decompose to discharge ammonia for NO xtransform; (ii) realize high as far as possible NO xconversion ratio.
Vehicle
The present invention is used for the gas extraction system of the vehicle that is equipped with internal combustion engine.Use the object lesson of the vehicle of internal combustion engine to be enumerated as: car, bus, lorry, locomotive, motorcycle, moped and heavy construction machinery etc.; Conveying arrangement, for example aircraft; Forest and agricultural machinery, for example plough, tractor, united reaper, chain saw truck (chainsaw truck) and lumber carrier; Boats and ships, for example ship, fishing boat and motorboat; Civil engineering machinery, for example crane, road roller and excavator; And generator.But application is not limited thereto.
Definition
Form of presentation used herein " oxidation catalyst ", particularly with reference to a first aspect of the present invention, the combination of ordinary representation substrate and oxidation catalyst (for example oxidation catalyst in a second aspect of the present invention).
Form of presentation used herein " multiple catalyst layer ", particularly with reference to a first aspect of the present invention, comprises " catalyst layer " and one or more " other catalyst layers "." catalyst layer " can be located immediately on one or more " other catalyst layers " or be arranged on one or more " other catalyst layers " upper (for example the superiors of " other catalyst layers "), or one or more intermediate layers (layer of for example non-" catalyst layer ") can be set between " catalyst layer " and one or more " other catalyst layers ".
Form of presentation used herein " catalyst surface layer side ", particularly with reference to a first aspect of the present invention, represents a side of the oxidation catalyst that is first exposed to waste gas, and it is outermost catalyst layer normally.
Form of presentation used herein " lower than a side of a described catalyst layer ", particularly with reference to a first aspect of the present invention, represents part or the region of oxidation catalyst between " catalyst layer " and " bearing basement ".
Form of presentation used herein " multiple catalyst layers comprise washcoat material, active metal and hydrocarbon adsorbent ", particularly with reference to a first aspect of the present invention, represent two or more catalyst layers, the wherein combination of all catalyst layers (layer is all) comprises washcoat material, active metal and hydrocarbon adsorbent.Therefore, washcoat material, active metal and hydrocarbon adsorbent needn't be present in each catalyst layer.But common each catalyst layer comprises washcoat material and at least one active metal or hydrocarbon adsorbent, is substantially made up of it, or is made up of it.Therefore, " catalyst layer " can comprise washcoat material and hydrocarbon adsorbent, is substantially made up of it, or is made up of it." one or more other catalyst layers " can comprise washcoat material and at least one active metal, are substantially made up of it, or are made up of it.But generally, each catalyst comprises washcoat material, active metal and hydrocarbon adsorbent, is substantially made up of it, or is made up of it.
Form of presentation used herein " amount of hydrocarbon adsorbent ", particularly with reference to a first aspect of the present invention, represents the total amount of the hydrocarbon adsorbent existing.Therefore, the total amount of the hydrocarbon adsorbent in " amount of the hydrocarbon adsorbent in this catalyst layer " expression " catalyst layer "." amount of hydrocarbon adsorbent in these one or more other catalyst layers " represents the total amount of the hydrocarbon adsorbent existing in all " other catalyst layers ".Conventionally, " amount of hydrocarbon adsorbent " conduct " quality of hydrocarbon adsorbent " (weight of for example hydrocarbon adsorbent) is measured.If there is the hydrocarbon adsorbent more than a kind, be somebody's turn to do so the total amount that " amount " represents the hydrocarbon adsorbent of all kinds existing.
Form of presentation used herein " concentration of active metal ", particularly with reference to a first aspect of the present invention, represents that the weight of active metal accounts for the ratio of the gross weight of each catalyst layer, is expressed as percentage by weight.The total concentration of one or more active metals in " concentration of active metal in this catalyst layer " expression " catalyst layer "." concentration of active metal in these one or more other catalyst layers " represents the total concentration of one or more active metals in all " other catalyst layers ".
Form of presentation used herein " in a described catalyst layer, the concentration of active metal equals the concentration of active metal in described one or more other catalyst layers ", particularly about a first aspect of the present invention, represent that concentration and its mean value only differ from 1%, preferably only differ from 0.1% with its mean value, or more preferably only differ from 0.01% with its mean value.Conventionally,, for intentional and object, this concentration is identical in the time that the method for measurement of concentration by standard normal is measured.
Form of presentation used herein " in a described catalyst layer, the amount of hydrocarbon adsorbent equals the amount of hydrocarbon adsorbent in described one or more other catalyst layers ", particularly about a first aspect of the present invention, expression amount and its mean value only differ from 1%, preferably only differ from 0.1% with its mean value, or more preferably only differ from 0.01% with its mean value.Conventionally,, for intentional and object, this amount is identical in the time that the quantity measuring method by standard normal is measured.
Form of presentation used herein " in a described catalyst layer, the weight of active metal equals the weight of active metal in described one or more other catalyst layers ", particularly about a first aspect of the present invention, represent that weight and its mean value only differ from 1%, preferably only differ from 0.1% with its mean value, or more preferably only differ from 0.01% with its mean value.Conventionally,, for intentional and object, this weight is identical in the time that the weight measurement method by standard normal is measured.
Any mentioning " weight of catalyst " used herein, particularly, with reference to a first aspect of the present invention, relate to the weight of the washcoat (for example comprising the washcoat of active metal, hydrocarbon adsorbent and washcoat material) being applied in carrier substrates.Conventionally, form of presentation used herein " catalyst layer ", particularly with reference to a first aspect of the present invention, has identical implication with form of presentation " the second washcoat " used in other aspects of the present invention.Similarly, form of presentation used herein " other catalyst layers ", particularly with reference to a first aspect of the present invention, has identical implication with form of presentation " the first washcoat " used in other aspects of the present invention.
Unclear for fear of causing, term " the second washcoat; wherein this second washcoat is arranged in the layer on the first washcoat " represents that this second washcoat can be located immediately on the first washcoat, or can between the first washcoat and the second washcoat, one or more intermediate layers be set.In DOC and NAC field, three layers of carbon monoxide-olefin polymeric are all known (referring to the GB Patent Application No. 1021649.7 that the name with this application people/assignee was submitted on December 21st, 2010 respectively).
Form of presentation used herein " substantially by ... form " be pointed material or step by the circumscription of the feature in claim or claim, and any other materials or the step of essential characteristic that can materially affect invention required for protection.It has form of presentation " by ... form " and " comprising " between implication.
Embodiment
Now will be by following non-limiting example explanation the present invention.
comparative example 1
1) prepare a catalyst layer (photons)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 12g/ rises carrier, and the concentration of active metal is 0.4wt%.The catalyst weight of every liter of carrier is 50g (active metal 0.2g).
2) prepare other catalyst layers (carrier side)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 30g/ rises carrier, and the concentration of active metal is 1.7wt%.The catalyst weight of every liter of carrier is 105g (active metal 1.785g).
3) be coated in bearing basement
First, apply NGK1.3 with the slurry for " other catalyst layers " and rise cellular bearing basement.Then calcine.Then, the slurry that is used for " catalyst layer " is coated in to " other catalyst layers ".Then calcine, comparative example 1 is provided.
comparative example 2
1) prepare a catalyst layer (photons)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The content of hydrocarbon adsorbent is that 12g/ rises carrier, and the concentration of active metal is 2wt%.The catalyst weight of every liter of carrier is set as 90g (active metal 1.8g).
2) prepare other catalyst layers (carrier side)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The content of hydrocarbon adsorbent is that 30g/ rises carrier, and the concentration of active metal is 0.3wt%.The catalyst weight of every liter of carrier is set as 65g (active metal 0.195g).
3) be coated in bearing basement
As in comparative example 1, obtain comparative example 2.
evaluation test 1
By the catalyst finally obtaining in stove 800 ℃ of heat treatments 20 hours, be then arranged in the blast pipe of four-in-line (4-in-line) Diesel engine.Use business diesel oil (JIS2), move instantaneous active testing, evaluate catalysts performance with actual waste gas.
test result 1
In table 1, provide result.The T of comparative example 2 50(the catalyst inlet temperature in the time that conversion ratio reaches 50%, T 50the lower expression catalyst performance of numerical value higher) low, this catalyst activity that shows comparative example 1 is higher than comparative example 2.
Table 1
COT 50:℃
Comparative example 1 188
Comparative example 2 202
comparative example 3
1) prepare a catalyst layer (photons)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 30g/ rises carrier, and the concentration of active metal is 1.7wt%.The catalyst weight of every liter of carrier is 105g (active metal 1.785g).
2) prepare other catalyst layers (carrier side)
Using as the Pt of active metal and Pd (2:1) and aluminium oxide (Al as washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 12g/ rises carrier, and the concentration of active metal is 0.4wt%.The catalyst weight of every liter of carrier is set as 50g (active metal 0.2g).
3) be coated in bearing basement
As in comparative example 1, obtain comparative example 3.
evaluation test 2
By the catalyst finally obtaining in stove 800 ℃ of heat treatments 20 hours, be then arranged in four-in-line Diesel engine.Use business diesel oil (JIS2), move instantaneous active testing, evaluate catalysts performance with actual waste gas.
test result 2
In table 2, provide result, shown that the catalyst activity of comparative example 3 is higher than comparative example 2.
Table 2
COT 50:℃
Comparative example 3 193
Comparative example 2 202
embodiment 1
1) prepare a catalyst layer (photons)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 24g/ rises carrier, and the concentration of active metal is 0.2wt%.The catalyst weight of every liter of carrier is 90g (active metal 0.18g).
2) prepare other catalyst layers (carrier material side)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 6g/ rises carrier, and the concentration of active metal is 2.2wt%.The catalyst weight of every liter of carrier is set as 90g (active metal 1.98g).
3) be coated in bearing basement
Use and obtain embodiment 1 with method identical described in comparative example 1.
comparative example 4
1) prepare a catalyst layer (photons)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 15g/ rises carrier, and the concentration of active metal is 1.2wt%.The catalyst weight of every liter of carrier is 90g (active metal 1.08g).
2) prepare other catalyst layers (carrier material side)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 15g/ rises carrier material, and the concentration of active metal is 1.2wt%.The catalyst weight of every liter of carrier is set as 90g (active metal 1.08g).
3) be coated in bearing basement
As described in comparative example 1, obtain comparative example 4.
comparative example 5
1) prepare a catalyst layer (photons)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " catalyst layer " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 6g/ rises carrier, and the concentration of active metal is 2.2wt%.The catalyst weight of every liter of carrier is 90g (active metal 1.98g).
2) prepare other catalyst layers (carrier material side)
Using as the Pt of active metal with as the aluminium oxide (Al of washcoat material 2o 3) and mix the slurry of preparation " other catalyst layers " as the zeolite of hydrocarbon adsorbent.The amount of hydrocarbon adsorbent is that 24g/ rises carrier, and the concentration of active metal is 0.2wt%.The catalyst weight of every liter of carrier is set as 90g (active metal 0.18g).
3) be coated in bearing basement
Use and obtain comparative example 5 with method identical described in comparative example 1.
evaluation test 3
By the catalyst finally obtaining in stove 800 ℃ of heat treatments 20 hours, be then arranged in four-in-line Diesel engine.Use business diesel oil (JIS2), move instantaneous active testing, evaluate catalysts performance with actual waste gas.
test result 3
In table 3, provide result, shown that the catalyst activity in embodiment 1 is significantly higher than comparative example 4 and 5.Therefore this result shows, in this catalyst layer and these other catalyst layers evenly catalyst weight relatively in, because catalyst structure has improved CO oxidation activity, wherein in this catalyst layer the amount of hydrocarbon adsorbent higher than the concentration that exists in these other catalyst layers, and in this catalyst layer the concentration of active metal lower than the concentration of aforementioned active metal in these other catalyst layers.
Table 3
COT 50:℃
Embodiment
1 180
Comparative example 4 199
Comparative example 5 198
embodiment 2
Preparation is coated with the substrate material all in one piece of 3wt%Cu/CHA zeolite
Under agitation add commercially available alumino-silicate CHA zeolite to Cu (NO 3) 2the aqueous solution in.By slurries filtration, then wash and be dried.Can repeat this program to obtain required content of metal.Final product is dry.After mixing, add adhesive and rheology modifier to form washcoat composition.
Disclosed method in request for utilization people/assignee's WO99/47260, with the aqueous slurry coating 400cpsi cordierite flow type substrate material all in one piece of 3wt%Cu/CHA zeolite sample, the method comprises the following steps: (a) will hold instrument and be placed in carrier top; (b) described in being metered into, holds in instrument the liquid component of scheduled volume, with (b) after elder generation (a) or first order of (a) after (b); (c) by implementing pressure or vacuum, described liquid component is drawn at least a portion of carrier, and almost all remaining in this carrier described amount.By dry the product of this coating (only from one end apply) and calcining subsequently, repeat this technique from the other end, make that all substrate materials all in one piece are all coated substantially, the junction between two coatings has small overlapping in the axial direction.This is aging 5 hours in 500 ℃ in air in stove through the substrate material all in one piece applying.Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.
embodiment 3
Prepare diesel oxidation catalyst A
Platinum nitrate and palladium nitrate are added in the aqueous slurry of particulate silica-aluminium oxide.β zeolite is added in this slurry, make its zeolite solid content that comprises <30 quality % to produce washcoat slurry.Use disclosed method in WO99/47260 that this washcoat slurry is joined on 400cpsi flow type substrate material all in one piece.This part adding is dry, then 500 ℃ of calcinings.Pt:Pd weight ratio in the first washcoat is 2:1.
Preparation the second moisture washcoat slurry as mentioned above, but use different platinum nitrate and the palladium nitrates of measuring.Use and apply the first washcoat same procedure used and this second washcoat slurry is joined to the ground floor top applying before.This second coating is dry, then 500 ℃ of calcinings.Pt:Pd weight ratio in the second washcoat is 1:1.6, and total PGM load capacity that the first washcoat and the second washcoat amount to is 1:1.Total washcoat load capacity that the first and second washcoat amount to is 3.0g in -3, total platinum group metal load capacity that the first washcoat and the second washcoat amount to is 120g ft -3.
Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
comparative example 6
Prepare diesel oxidation catalyst B
Platinum nitrate and palladium nitrate are added in the aqueous slurry of aluminium oxide of particle stabilizedization.β zeolite is added in this slurry to the zeolite solid content that makes it comprise <30 quality %.Use the method identical with embodiment 3 that this washcoat slurry is joined on 400cpsi flow type substrate material all in one piece.By dry this part through applying, then 500 ℃ of calcinings.Pt:Pd weight ratio in the first washcoat is 2:1.
By being added to, platinum nitrate in particulate oxidation aluminum slurry, prepares the second moisture base coating slurry.β zeolite is added in this slurry to the zeolite solid content that makes it comprise <30 quality %.Use the ground floor top applying before this washcoat being joined with identical method above.Then this second washcoat is dry, and by this part 500 ℃ of calcinings.Pt:Pd weight ratio in the second washcoat is 1:0, total washcoat load capacity 3.0g in that the first washcoat and the second washcoat amount to -3, the major part of washcoat load capacity is in lower floor.Total platinum group metal load capacity that the first and second washcoat amount to is 85g ft -3.The Pt:Pd weight ratio that the first washcoat and the second washcoat amount to is 4:1.Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
embodiment 4
Prepare diesel oxidation catalyst C
Platinum nitrate is added in the aqueous slurry of aluminium oxide.β zeolite is added in this slurry to the zeolite solid content that makes it comprise <30 quality %.Use the method identical with embodiment 2 that this washcoat slurry is joined on 400cpsi flow type substrate material all in one piece.This part adding is dry, then 500 ℃ of calcinings.The first washcoat has the Pt:Pd weight ratio of 1:0.
By being added to, platinum nitrate and palladium nitrate in particulate oxidation aluminum slurry, prepare the second moisture washcoat slurry.β zeolite is added in this slurry to the zeolite solid content that makes it comprise <30 quality %.The ground floor top applying before this second washcoat slurry is joined.This second washcoat is dry, and 500 ℃ of calcinings.The second washcoat has the Pt:Pd ratio of 2:1.The Pt:Pd weight ratio that the first washcoat and the second washcoat amount to is 4:1, and total platinum group metal load capacity of two-layer total is 85g ft -3.Total washcoat load capacity of first and second layers of total is 3.0g in -3, the major part of washcoat load capacity is in the second washcoat.
Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
embodiment 5
System testing
This test is carried out in the first synthetic catalyst active testing (SCAT) laboratory reaction device shown in Fig. 1, wherein the aging core of the Cu/CHA zeolite scr catalysts through applying of embodiment 1 is arranged in the pipeline in core downstream of diesel oxidation catalyst (DOC) B (according to comparative example 6) or C (according to embodiment 4).Make syngas mixture pass through this pipeline with the speed of 6 liters/min.Use stove with the catalyst outlet temperature of 900 ℃, this DOC sample to be heated to (or " aging ") 2 hours at steady temperature.This SCR catalyst is arranged on to the downstream of DOC sample, and the length of tube exporting by regulating stove between SCR entrance holds it in the catalyst temperature of 300 ℃ in aging technique process, but also can optionally use oil-to-water heat exchanger chuck.Use the thermocouple measurement temperature (T that is applicable to location 1and T 2).The admixture of gas using in ageing process is 40% air, 50%N 2, 10%H 2o.
After DOC is aging, from a SCAT reactor, shift out this SCR catalyst, and be inserted in the 2nd SCAT reactor, be used in particular for testing the NH of this aged samples 3-SCR activity.Then use syngas mixture (O 2=10%; H 2o=5%; CO 2=7.5%; CO=330ppm; NH 3=400ppm; NO=500ppm; NO 2=0ppm; N 2=surplus, is used 0.8 α value (NH 3: NO xratio), the NO of the maximum possible that makes it possible to obtain xconversion ratio is 80%) test SCR catalyst is the SCR activity of 500 ℃, by obtained NO xconversion ratio is depicted on the block diagram in accompanying drawing 2 with respect to temperature.This figure has weighed the competition between reaction (9) and reaction (5) substantially, and has therefore weighed reaction (9) by consuming the required obtainable NH of SCR reaction (reaction (5)) 3to NO xthe influence degree of conversion ratio.
The result presenting from Fig. 2 can find out, DOC C (according to embodiment 6) has kept the more a high proportion of NO than DOC B (according to comparative example 6) xactivity of conversion.The inventor is interpreted as this conclusion, this shows under test condition used, compared with the DOC C of opposed that there is the Pt:Pd weight ratio of 2:1 with skin, Pt is more easily from having the outer volatilization of DOC B of Pt:Pd weight ratio of 1:0, but in two kinds of situations, total Pt:Pd weight ratio of two-layer total equates, is 4:1.
embodiment 6
Preparation is coated with the substrate material all in one piece of 5wt%Fe/ β zeolite
Under agitation add commercially available β zeolite to Fe (NO 3) 3the aqueous solution in.After mixing, add adhesive and rheology modifier to form washcoat composition.
Disclosed method in request for utilization people/assignee's WO99/47260, as herein above described in embodiment 2, with the aqueous slurry coating 400cpsi cordierite flow type substrate material all in one piece of 5wt%Fe/ β zeolite sample.By dry this coated product (only from one end apply) and calcining subsequently, repeat this technique from the other end, make that all substrate materials all in one piece are all coated substantially, the junction between two coatings has small overlapping in the axial direction.Cut the core body of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.
comparative example 7
Prepare the only catalysis wall-flow filter of Pt
Preparation is ground to the washcoat composition of the mixture of alumina particle, platinum nitrate, adhesive and the rheology modifier of relatively high size distribution comprising in deionized water.The methods and apparatus disclosed in request for utilization people/assignee's WO2011/080525, use carbon monoxide-olefin polymeric with 0.2g/in 3washcoat load capacity apply aluminium titanates wall-flow filter to 5g/ft 3final total Pt load capacity, wherein will and have a mind at first end the upstream extremity that orientation uses the washcoat that comprises platinum nitrate and particulate alumina to have a mind to from it to the passage of upstream side apply 75% of its total length; To also have a mind to be orientated use the washcoat identical with access road to apply 25% of its total length to the passage in downstream in opposite segments., the method comprises the following steps: (i) cellular monolith substrates is kept to vertical substantially; (ii) liquid of predetermined is introduced in this substrate by the openend of the passage of this substrate lower end; (iii) hydraulic seal of introducing is remained in this substrate; (iv) substrate that comprises kept liquid is inverted; (v) in the inverted lower end of this substrate, the openend of the passage to this substrate applies vacuum, to extract this liquid along the passage of this substrate.This carbon monoxide-olefin polymeric is coated in filter passage from first end, then that the filter through applying is dry.Then the filter of the drying applying from first end is put upside down, repeated the method to apply identical catalyst to filter passage from the second end, be then dried and calcine.
Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
embodiment 7
The catalysis wall-flow filter that preparation comprises 1:1wt%Pt:Pd
Use the filter applying with method identical in comparative example 7 preparation, be just applied to the access road of this filter and the washcoat of exit passageway and except platinum nitrate, also comprise palladium nitrate.Washcoat load in entrance and exit passage to reach 5g/ft on inner surface and outer surface 3pt, 5g/ft 3the mode of Pd is carried out, and total PGM load capacity is 10g/ft 3.
Cut the core of 1 inch of (2.54cm) diameter × 3 inchage from the goods that complete.The part obtaining is described as " fresh ", not aged.
embodiment 8
The catalysis wall-flow filter that preparation comprises 5:1wt%Pt:Pd
Use the filter applying with method identical in comparative example 7 preparation, be just applied to the access road of this filter and the washcoat of exit passageway and except platinum nitrate, also comprise palladium nitrate.The washcoat load of entrance and exit passage to reach 5g/ft on inner surface and outer surface 3pt, 1g/ft 3the mode of Pd is carried out, and total PGM load capacity is 6g/ft 3.
Cut the core of 1 inch of (2.54cm) diameter × 3 inchage from the goods that complete.The part obtaining is described as " fresh ", not aged.
embodiment 9
System testing
This test is carried out in the first synthetic catalyst active testing (SCAT) laboratory reaction device shown in Fig. 1, wherein the fresh core of the Fe/ β zeolite scr catalysts through applying of embodiment 2 is arranged in the pipeline in core downstream of the catalysis wall-flow filter of comparative example 7 or embodiment 7 or 8.Make syngas mixture with 30,000hr -1catalyst piston discharge capacity (swept volume) through this pipeline.Use stove with the filter inlet temperature of 900 ℃, this catalysis wall-flow filter sample to be heated to (or " aging ") 60 minutes at steady temperature, entrance SCR catalyst temperature is 300 ℃ during this period.Using air (heat exchanger) or magnetism servo-electric motor water-cooling between filter and SCR catalyst, to realize temperature reduces.Admixture of gas in ageing process is 10%O 2, 6%H 2o, 6%CO 2, 100ppm CO, 400ppm NO, 100ppm be as the HC of C1 meter, surplus is N 2.
After aging, from a SCAT reactor, take out this SCR catalyst, and be inserted in the 2nd SCAT reactor, be used in particular for testing the NH of this aged samples 3-SCR activity.Then use syngas mixture (O 2=14%; H 2o=7%; CO 2=5%; NH 3=250ppm; NO=250ppm; NO 2=0ppm; N 2=surplus) measure SCR catalyst the SCR activity of 150,200,250,300,350,450,550 and 650 ℃, by the obtained NO for each temperature data points xconversion ratio is depicted in accompanying drawing 2 with respect to temperature.This figure has weighed the competition between reaction (9) and reaction (5) substantially, and has therefore weighed reaction (9) by consuming the required obtainable NH of SCR reaction (reaction (5)) 3to NO xthe influence degree of conversion ratio.
Result is plotted in Fig. 3.With reference to Fig. 3, can see have 1:0 Pt:Pd weight ratio catalysis soot filter (being comparative example 7) afterwards aging Fe/ β zeolite scr catalysts there is significantly reduced total NO compared with fresh sample xactivity of conversion.The catalysis soot filter of the Pt:Pd weight ratio with 5:1 of embodiment 8 has the NO of raising compared with comparative example 7 xactivity of conversion.But the embodiment 7 with the Pt:Pd weight ratio of 1:1 has and the clear and definite similarly performance of not aged SCR catalyst.In the situation that upstream does not exist any catalyst, there is no and see activity decreased (result is not shown) between the Fe/ beta catalyst after aging 1 hour at fresh Fe/ beta catalyst with at 300 ℃.
embodiment 10
Further Pt:Pd weight ratio research
Two kinds of diesel oxidation catalysts of following further preparation:
diesel oxidation catalyst D
Be prepared as follows individual layer DOC.Platinum nitrate and palladium nitrate are added in the slurry of silica-alumina.In this slurry, add β zeolite, the zeolitic solid content that makes it comprise <30 quality %.Use the method for embodiment 3 that this washcoat slurry is joined in the substrate of 400cpsi flow type.This part adding is dry, then 500 ℃ of calcinings.Total platinum group metal load capacity in this washcoat is 60g ft -3, total Pt:Pd weight ratio is 4:1.
Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
diesel oxidation catalyst E
Be prepared as follows individual layer DOC.Platinum nitrate and palladium nitrate are added in the slurry of silica-alumina.In this slurry, add β zeolite, the zeolitic solid content that makes it comprise <30 quality %.Use the same procedure used with DOC D that this washcoat slurry is joined in the substrate of 400cpsi flow type.This part adding is dry, then 500 ℃ of calcinings.Total PGM load capacity in this individual layer DOC is 120g ft -3, total Pt:Pd weight ratio is 2:1.Cut the core of 1 inch of (2.54cm) diameter × 3 inch (7.62cm) length from the goods that complete.The part obtaining is described as " fresh ", not aged.
According to two kinds of catalyst of the program test of listing in embodiment 5.With reference to the Fig. 4 that the results are shown in of control sample (further not aging through aging SCR catalyst in DOC D or DOC E downstream).
conclusion
All in all, embodiment 9 shown in Fig. 3 together with embodiment 7 and 8 and the result of comparative example 7 show, the Pt:Pd weight ratio between 1:1 and 5:1 is conducive to reduce and evaporate into from the catalyst that comprises platinum group metal the NO that downstream SCR catalyst causes by platinum group metal (being mainly platinum) xthe problem of activity of conversion loss.
Embodiment shown in Fig. 45 and 10 results together with diesel oxidation catalyst D and E show, for the aging SCR catalyst in DOC downstream of Pt:Pd gross weight ratio with 2:1, with the 72%NO of control sample xactivity of conversion (has 69% NO at the aging afterwards SCR catalyst of the DOC that uses same program at 1:1Pt:Pd gross weight ratio (not describing) herein xactivity of conversion) compare NO xthe loss of activity of conversion is relatively little, is 67%NO xactivity of conversion.But in the time that total Pt:Pd weight ratio is brought up to 4:1, SCR activity is significantly reduced to 48%.
Therefore the inventor sums up, and has border in about 2:1Pt:Pd gross weight than place, and Pt volatilization more easily occurs in the situation that exceeding it.Therefore, by being limited to the total Pt:Pd weight of overall 2:1 in DOC and being limited in the second washcoat≤the Pt:Pd weight ratio of 2:1, the Pt in DOC is not easy volatilization and moves to the SCR catalyst in downstream.
For avoiding any uncertain, the full content of any and All Files of quoting is herein all by reference to introducing in the application.

Claims (36)

1. for the hydrocarbon (HC) of oxidation processes waste gas and the oxidation catalyst of carbon monoxide (CO), this oxidation catalyst comprises bearing basement and loads on the multiple catalyst layers in this bearing basement, wherein the plurality of catalyst layer comprises washcoat material, active metal and hydrocarbon adsorbent, and one of them catalyst layer is positioned at catalyst surface layer side, one or more other catalyst layers are positioned at than in the low side of a described catalyst layer; Wherein:
(a) in a described catalyst layer, the amount of hydrocarbon adsorbent is greater than the amount of hydrocarbon adsorbent in described one or more other catalyst layers, and in a described catalyst layer, the concentration of active metal is equal to or less than the concentration of active metal in described one or more other catalyst layers; Or
(b) in a described catalyst layer, the amount of hydrocarbon adsorbent equals the amount of hydrocarbon adsorbent in described one or more other catalyst layers, and in a described catalyst layer, the concentration of active metal is less than the concentration of active metal in described one or more other catalyst layers.
2. oxidation catalyst according to claim 1, it is made up of two catalyst layers.
3. according to the oxidation catalyst of claim 1 or 2, wherein hydrocarbon adsorbent is zeolite.
4. according to oxidation catalyst in any one of the preceding claims wherein, wherein this catalyst layer has 0.05-3.00g in -3hydrocarbon adsorbent concentration.
5. according to oxidation catalyst in any one of the preceding claims wherein, wherein hydrocarbon adsorbent is 10:1-1.1:1 with the ratio of the amount in described one or more other catalyst layers in a described catalyst layer.
6. according to the oxidation catalyst described in any one in claim 1-4, in wherein said one or more other catalyst layers, there is no hydrocarbon adsorbent.
7. according to oxidation catalyst in any one of the preceding claims wherein, one of them catalyst layer or the second washcoat have the hydrocarbon adsorbent concentration of the 10-50wt% of this layer.
8. according to oxidation catalyst in any one of the preceding claims wherein, wherein active metal is platinum, palladium or its mixture.
9. according to oxidation catalyst in any one of the preceding claims wherein, wherein these one or more other catalyst layers have 0.05-3.5g in -3active metal concentration.
10. according to oxidation catalyst in any one of the preceding claims wherein, wherein active metal is 1:50-1:1.1 with the ratio of the concentration in described one or more other catalyst layers in a described catalyst layer.
11. according to oxidation catalyst in any one of the preceding claims wherein, and wherein this catalyst layer has the active metal concentration of 0.01-5wt%.
12. according to oxidation catalyst in any one of the preceding claims wherein, and wherein washcoat material is to be selected from SiO 2, Al 2o 3, CeO 2and TiO 2carrier material.
13. according to oxidation catalyst in any one of the preceding claims wherein, and it is catalytic substrate material all in one piece, and wherein this bearing basement is substrate material all in one piece, and a described catalyst layer is the first washcoat, and one of described other catalyst layers are the second washcoat.
14. oxidation catalysts according to claim 13, wherein the first washcoat comprises and contains platinum and the carbon monoxide-olefin polymeric at least one carrier material of platinum, the second washcoat comprises and contains platinum and palladium and the carbon monoxide-olefin polymeric at least one carrier material of platinum and palladium, and wherein in the second washcoat the weight ratio of platinum and palladium be≤2.
The 15. catalytic substrate materials all in one piece for the treatment of the waste gas from fuel-sean engine exhaust, it is included in the oxidation catalyst on substrate material all in one piece, this catalytic substrate material all in one piece comprises the first washcoat and the second washcoat, wherein the second washcoat is arranged in the layer on the first washcoat, wherein the first washcoat comprises and contains platinum and the carbon monoxide-olefin polymeric at least one carrier material of platinum, wherein the second washcoat comprises and contains platinum and palladium and the carbon monoxide-olefin polymeric at least one carrier material of platinum and palladium, and wherein in the second washcoat, the weight ratio of platinum and palladium is≤2.
16. according to the catalytic substrate material all in one piece described in any one in claim 13-15, and wherein this substrate material all in one piece is flow type substrate material all in one piece.
17. according to the catalytic substrate material all in one piece described in any one in claim 13-16, and wherein the second washcoat comprises platinum and palladium, and wherein the first washcoat comprises platinum and the palladium higher than the Pt:Pd weight ratio in the second washcoat.
18. according to the catalytic substrate material all in one piece described in any one in claim 13-17, and the Pt:Pd weight ratio that wherein the first washcoat and the second washcoat amount to is >=1:1.
19. catalytic substrate materials all in one piece according to claim 18, the Pt:Pd weight ratio that wherein the first washcoat and the second washcoat amount to is >=2:1.
20. according to the catalytic substrate material all in one piece described in any one in claim 13-19, and the Pt:Pd weight ratio that wherein the first washcoat and the second washcoat amount to is≤10:1.
21. according to the catalytic substrate material all in one piece described in any one in claim 13-20, and wherein the first washcoat comprises the 25-75wt% that amounts to the total platinum group metal existing in the first washcoat and the second washcoat.
22. according to the catalytic substrate material all in one piece described in any one in claim 13-21, and wherein at least one carrier material of the first washcoat or the second washcoat comprises the freely metal oxide of the following group forming of choosing: the Ceria-zirconia mixed oxide of zirconia, cerium oxide, titanium oxide and the optional stabilisation of the aluminium oxide of optional stabilisation, amorphous silica-aluminium oxide, optional stabilisation or molecular sieve or its mixture of two or more arbitrarily.
23. according to the catalytic substrate material all in one piece described in any one in claim 13-22, wherein in the first washcoat and the second washcoat one of at least comprise each washcoat≤molecular sieve of 30wt%.
24. according to the catalytic substrate material all in one piece described in any one in claim 13-23, and wherein the first washcoat and the second washcoat washcoat load capacity in is separately selected from 0.1-3.5g in individually -3scope.
25. according to the catalytic substrate material all in one piece described in any one in claim 13-24, and wherein this oxidation catalyst is diesel oxidation catalyst or NO xadsorption catalyst.
26. gas extraction system for fuel-sean internal combustion engine, this system comprises according to the first catalytic substrate material all in one piece described in any one in claim 13-25.
27. gas extraction system according to claim 26, it comprises the second catalytic substrate material all in one piece that comprises SCR (SCR) catalyst, this second catalytic substrate material all in one piece is arranged on the downstream of the first catalytic substrate material all in one piece.
28. gas extraction system according to claim 27, it is included between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece for nitrogenous reducing agent being injected to the injector of waste gas.
29. according to the gas extraction system described in claim 27 or 28, it comprises the 3rd catalytic substrate material all in one piece, wherein the substrate material all in one piece of the first catalytic substrate material all in one piece is flow type substrate material all in one piece, wherein the 3rd catalytic substrate material all in one piece is the filtration substrate material all in one piece with inlet surface and exit surface, and wherein inlet surface and exit surface are separated by cell structure, the 3rd catalytic substrate material all in one piece comprises oxidation catalyst and between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece.
30. gas extraction system according to claim 29, it is included between the first catalytic substrate material all in one piece and the second catalytic substrate material all in one piece for nitrogenous reducing agent being injected to the injector of waste gas, and wherein this injector that is used for nitrogenous reducing agent to inject waste gas is through arranging nitrogenous reducing agent is injected to waste gas between the 3rd catalytic substrate material all in one piece and the second catalytic substrate material all in one piece.
31. according to the gas extraction system described in claim 27 or 28, it comprises the 3rd substrate material all in one piece, wherein the 3rd substrate material all in one piece is the filtration substrate material all in one piece with inlet surface and exit surface, wherein inlet surface and exit surface are separated by cell structure, and the 3rd substrate material all in one piece is positioned at the downstream of the second catalytic substrate material all in one piece.
32. gas extraction system according to claim 31, wherein the 3rd substrate material all in one piece comprises oxidation catalyst.
33. according to the gas extraction system described in any one in claim 27-32, and wherein the second catalytic substrate material all in one piece is the filtration substrate material all in one piece with inlet surface and exit surface, and wherein inlet surface and exit surface are separated by cell structure.
34. according to the gas extraction system described in any one in claim 29-33, and wherein filtering substrate material all in one piece is wall-flow filter.
35. fuel-sean internal combustion engines, are used in particular for vehicle, and it comprises according to the gas extraction system described in any one in claim 26-34.
36. reduce or prevent that in the gas extraction system of fuel-sean internal combustion engine, SCR (SCR) catalyst becomes the method for platinosis, this platinum can evaporate from comprising the first washcoat that contains platinum and at least one carbon monoxide-olefin polymeric for the carrier material of platinum in the time that this carbon monoxide-olefin polymeric that comprises platinum is exposed to relative extreme condition, this first washcoat is positioned on the substrate material all in one piece of SCR catalyst upstream, this relatively extreme condition comprises higher temperature, the method comprise by the platinum of volatilization be captured in be arranged on the first washcoat layer the second washcoat, this second washcoat comprises and contains platinum and palladium and the carbon monoxide-olefin polymeric at least one carrier material of platinum and palladium, and wherein in the second washcoat, the weight ratio of platinum and palladium is≤2.
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